REACTION OF LIE(SIME3)2 WITH COMPOUNDS CONTAINING 4-MEMBERED CORES OF THE GENERAL FORMULA MEM(CL) (M = IN, E = AS, P, M = GA, E = AS) - NOVEL REARRANGEMENT REACTIONS TO FORM THE ADDUCTS R3M-BULLET-AS(SIME3)3 (R = ME3SICH2, M = IN, R = PH, M = GA)

The 1:1 reactions of R2ME(SiMe3)2M(R)2Cl with LiE(SiMe3)2 (R = Me3SiCH2, M = In, E = P; R = Me3SiCH2, M = In, E = As; R = Me3SiCH2, M = Ga, E = As; R = Ph, M = Ga, E = As) result in the formation of species containing MEME core structures as verified by comparison of C-13 and H-1 NMR spectra, and melting points, to those obtained for authentic samples prepared previously. When reactions were carried out involving R2ME(SiMe3)2M(R)2Cl and LiE'(SiMe3)2 (R = Me3SiCH2, M = In, E = P, E' = As; R = Ph, M = Ga, E = As, E' = P), novel rearrangements resulted to form R3M.As(SiMe3)3 [R = Me3SiCH2, M = In (1) or R = Ph, M = Ga (2)]. Both 1 and 2 are formed via the homoleptic redistribution of the substituents on both the metal center and the pnictide. Compound 1 belongs to the rhombohedral system, space group R3 with cell constants a = 16.185 (5) angstrom, c = 12.265 (4) angstrom, V = 2782 (2) angstrom3, and Z = 3. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c with cell constants a = 18.867 (5) angstrom, b = 19.307 (2) angstrom, c = 20.926 (6) angstrom, beta = 123.27 (1)-degrees, V = 6373 (5) angstrom3, and Z = 8.